Oxidized product of water-insoluble



Patented Dec. 31, 1935 PATENT; OFFICE OXIDIZED PRODUCT OFWATER-INSOLUBLE HYDROXYLATED FATTY ACIDS Melvin De Groote, St. Louis,and Bernhard Keiser, Webster Groves, Mo., assignors to TretoliteCompany, Webster Groves, Mo., a corporation of Missouri No Drawing.Application November 12,1934, Serial No. 752,721

4 Claims.

an oxidation product or products derived by blowing the hydrolyticproducts (hydroxylated fatty acids), obtained by subjecting a linseedoil-type fatty acid sulfation mass to hydrolysis. These products arereferred to as oxidation products because they are somewhat similar toconventional oxidized or blown oils, and are obtained by oxidizing orblowing certain hydroxylated fatty acids, hereinafter described, bymeans of air or p 20 oxygen. The fatty products or hydroxylated fattyacids which are subjected to oxidation, are derived by the hydrolysis ofthe sulfation mass obtained by treating linseed oil-type fatty acids,such as linseed oil fatty acids or perilla oil fatty 23 acids, withsulfuric acid, at approximately 35 to 54 C. Linseed oil fatty acids orperilla oil fatty acids are obtained from linseed oil or from perillaoil, respectively, by the usual method of fat splitting, such as aTwitchell process.

It is customary tooxidize or blow certain nondrying oils, such as castoroil or red oil, by means of dry or moist air or oxygen. Castor oil isused most frequently for this purpose. Similarly, the said procedure isemployed to blow semi-drying oils such as cottonseed oil. The productsso obtained have found use in various arts in the past, such as in themanufacture of lubricants, or as plasticizers in the manufacture ofartificial leather, etc. Blown or oxidized castor oil has found use inthe demulsification of crude oil.

Oxidation or blowing of a true drying oil such as linseed oil or perillaoil yields a leathery mass or a product such as linoleum. It isunsatisfactory to attempt to produce-a blown oil solely from 45 truedrying oils.

' the literature that blown oils can be produced from linseed oil andthe like. Blown oils, if produced from linseed oil, at the most,represent nothing more than an incipient oxidation, and do not representa blown oil which is basically changed in chemical characteristics inthe manner corresponding to the change which occurs in blown castor oil.Reference is made to U. S.

55 Patent No- ,929,399, o F dated October 3,

Statements have appeared in 1933, in which the chemical characteristicsof a truly blown castor oil are indicated.

' The same chemical activity which results in a stringy or leatheryproduct, of relatively worthless properties, when one attempts'todrastically blow or oxidize linseed oil, is also responsible for theinability to sulfonate or sulfate linseed oil so as to yield anacceptable and valuable sulfonation product. It is impractical to treatlinseed oil with sulfuric acid so as to produce a Turkey red oilsubstitute suitable for the purposes for which Turkey red oil isordinarily employed.

In U. S. Patent No. 1,745,221, to Bernhard Keiser, dated January 28,1930, there is disclosed a method of making a hydroxylated sulfationproduct from linseed oil or perilla oil, by sulfation of the fatty acidsderived from" the glycerides. Briefly stated, it is disclosed in thatpatent that the fatty acids of these true drying oils, for some fated soas to yield a product akin to Turkey red oil. The process theredisclosed contemplates the converting of linseed oil or perilla oil intothe fatty acids by means of the well known Twitchell process, or anyother acceptable process 'conventionally employed for fat splitting. Thefattyacids thus obtained are sulfated or sulfonated with 64 Baumsulfuric acid, at a temperature. not to exceed 54 C.

In the method employed to produce our new material or composition ofmatter, we follow the same procedure as disclosed in said Keiser patent,so far as the sulfation goes. After the sulfation of linseed oil fattyacids, for example, with approximately 50% by weight of 64 Baum sulfuricacid at not over 54 C., we wash the product with an approximately equalweight of water and allow the mixture to stand until two layers form.The lower layer is withdrawn and discarded. This washing process may berepeated, if desired. The upper fatty layer, consisting largely oflinseed oil fatty acid sulfates, perhaps already partially hydrolyzed,is water-soluble in a 10% solution. It is diluted with an approximatelyequal volume of water, and then treated with live steam until it is 5 nolonger water-soluble, and until it is substantially free from allcombined sulfurtrioxide. This product, so obtained, is. the hydrolyticproduct derived by decomposition of the materials obtained by sulfationof linseed oil fatty acids. For the sake of brevity, we refer to theseparticular products as the hydroxylated fatty acids. It is to be notedthat the expression hydroxylated fatty acids, refers solely to theproducts thus obtained by hydrolysis of the sulfation mass ob- 55unknown reason, can be readily sulfonated or sul- 20 tained by treatmentof. linseed oil fatty acids or perilla oil fatty acids, with sulfuricacid, under conditions to yield a water-soluble, non-stringy mass. Toprevent corrosion, any acidity to methyl orange indicator can, beneutralized with a suitable base, such as caustic soda.

We oxidize or blow these hydroxylated fatty acids in the conventionalmanner with either moist or dry air, or moist or dry oxygen. We preferto use air with its normal content of moisture. One procedure which wehave found suitable is to heat these hydroxylated fatty acids toapproximately C., and then blow with air for several hours, possibly asmuch as fifteen hours, in order to give a heavy bodied fatty product ofincreased viscosity and increased specific gravity. Such a product issubstantially free from any stringiness. The product thus obtained iseffective as a demulsifying agent for crude oil .emulsions of thewater-in-oil type, especially after dilution with a solvent, such asxylene. It is possible that such product may be used advantageously inthe arts where blown oils of the conventional type have been found to beof value. It is understood, of course, that in hydrolyzing the sulfationmass previously described, that there may be added a small amount ofTwitchell agent or any other material which would hasten the hydrolyticreactions. It is also understood that a certain amount of unsulfonatedor nonhydroxylated fatty material may be present in the sulfation mass,and remain in the finally washed product.

Having thus described our invention, what we claim as new and desire tosecure by Letters Patent is:

l. A new composition of matter, consisting of the oxidized productderived by blowing until substantial oxidation takes place,water-insoluble hydroxylated fatty acids, obtained by the hydro- -lyticdecomposition of linseed oil type fatty acid .lytic decomposition oflinseed oil fatty acid sulfates.

3. A method of producing a new composition of matter of the kinddescribed, characterized by blowing until substantial oxidation takesplace, water insoluble, hydroxylated fatty acids, obtained by thehydrolyticdecomposition of linseed oil type fatty acid sulfates.

4. A method of producing a new composition of matter of the kinddescribed, characterized by blowing until substantial oxidation takesplace, water insoluble, hydroxylated fatty acids, obtained by thehydrolytic decomposition of linseed oil fatty acid sulfates.

MELVIN DE GROOTE. BERNHARD KEISER.

